N-oxygenated arylpyrrole intermediates for insecticidal, acaricidal and nematicidal agents

ABSTRACT

Novel N-oxygenated arylpyrrole compounds which are effective for the control of insects, acarids and nematodes are described. A method for the insecticidal, acaricidal and nematicidal use of said compounds and a method for the preparation of said compounds are presented.

BACKGROUND OF THE INVENTION

This is a division of co-pending application Ser. No. 07/818,319, filedon Jan. 8, 1992, U.S. Pat. No. 5,232,979, which is a division ofapplication Ser. No. 07/447,726, filed Dec. 8, 1989, now U.S. Pat. No.5,102,904, issued Apr. 7, 1992.

SUMMARY OF THE INVENTION

The present invention describes N-oxygenated arylpyrrole compounds thatare highly effective insecticidal, acaricidal and nematicidal agentsuseful for the control of insect, acarid and nematode pests and forprotecting agronomic crops, both growing and harvested, against theravages of said pests.

The N-oxygenated arylpyrrole compounds of the present invention have thestructural formula I: ##STR1## wherein X is H, F, Cl, Br, I, CF₃ or CN;

Y is H, F, Cl, Br or I;

W is CN or NO₂ ;

A is H, C₁ -C₄ alkyl or C₂ -C₄ monohaloalkyl, each optionallysubstituted with from one to three additonal halogen atoms, one cyano,one hydroxy, one or two C₁ -C₄ alkoxy groups each optionally substitutedwith one to three halogen atoms, one C₁ -C₄ alkylthio, one C₁ -C₄carbalkoxy, one C₁ -C₆ alkylcarbonyloxy, one C₂ -C₆ alkenylcarbonyloxy,one benzenecarbonyloxy, or chloro, dichloro, or methyl substitutedbenzenecarbonyloxy, one phenyl optionally substituted with C₁ -C₃ alkoxyor with one to three halogen atoms, one phenoxy optionally substitutedwith one to three halogen atoms, or one benzyloxy optionally substitutedwith one halogen substituent;

C₃ -C₅ alkenyl optionally substituted with one to three halogen atoms;

C₃ -C₅ alkynyl optionally substituted with one halogen atom; or ##STR2##D is C₁ -C₆ alkyl, C₂ -C₄ alkenyl, C₁ -C₄ alkoxy, phenyl or phenoxy, alloptionally substituted with 1 to 3 halogens, di-(C₁ -C₄ alkyl)amino orN(CH₂)_(m) ;

m is an integer of 3, 4, 5, 6 or 7;

L is H, F, Cl or Br; and

M and R are each independently H, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₃alkylthio, C₁ -C₃ alkylsulfinyl, C₁ -C₃ alkylsulfonyl, cyano, F, Cl, Br,I, nitro, CF₃, R₁ CF₂ Z, R₂ CO or NR₃ R₄ ; and when M and R are onadjacent positions and taken with the carbon atoms to which they areattached they may form a ring in which MR represents the structure:##STR3## Z is S(O)_(n) or O; R₁ is H, F, CHF₂ CHFCl or CF₃ ;

R₂ is C₁ -C₃ alkyl, C₁ -C₃ alkoxy or NR₃ R₄ ;

R₃ is H or C₁ -C₃ alkyl;

R₄ is H, C₁ -C₃ alkyl or R₅ CO;

R₅ is H or C₁ -C₃ alkyl; and

n is an integer of 0, 1 or 2.

DETAILED DESCRIPTION OF THE INVENTION

The compounds of the present invention are excellent insecticidal,acarididal and nematicidal agents. The invention provides a method forcontrolling undesirable pests by contacting the pests, their breedinggrounds, food supply or habitat with a pesticidally effective amount ofan N-oxygenated arylpyrrole compound. Preferred groups of N-oxygenatedarylpyrroles of the present invention are illustrated by formula II,formula III and formula IV. ##STR4## wherein A, L, M, R, W, X and Y areas described above.

Preferred N-oxygenated arylpyrroles of the invention are those in which

A is hydrogen or C₁ -C₄ alkyl optionally substituted with one C₁ -C₄alkoxy group;

W is CN or NO₂ ;

X is Cl, Br or CF₃ ;

Y is Cl or Br;

R is F, Cl, Br, CF₃ or OCF₃ ;

M is H, F, Cl or Br; and

L is H or F.

The N-oxygenated arylpyrrole compounds of formula I, wherein A ishydrogen, W is CN and X, Y, L, M and R are as described above, may beprepared by reacting methyl benzoate or a substituted methyl benzoaterepresented by the structural formula V: ##STR5## wherein L is H, F, Clor Br; and

M and R are each independently H, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₃alkylthio, C₁ -C₃ alkylsulfinyl, C₁ -C₃ alkylsulfonyl, cyano, F, Cl, Br,I, nitro, CF₃, R₁ CF₂ Z, R₂ CO or NR₃ R₄ ; and when M and R are onadjacent positions and taken with the carbon atoms to which they areattached they may form a ring in which MR represents the structure:##STR6## Z is S(O)_(n) or O; R₁ is H, F, CHF₂ CHFCl or CF₃ ;

R₂ is C₁ -C₃ alkyl, C₁ -C₃ alkoxy or NR₃ R₄ ;

R₃ is H or C₁ -C₃ alkyl;

R₄ is H, C₁ -C₃ alkyl or R₅ CO;

R₅ is H or C₁ -C₃ alkyl; and

n is an integer of 0, 1 or 2;

with at least an equivalent amount of an acetal of cyanopropionaldehydein the presence of at least an equivalent amount of sodium hydride togive the appropriately substituted 3-benzoyl-3-cyano-1-propionaldehydeacetal represented by the structural formula VI. The propionaldehydeintermediate is then reacted with at least an equivalent amount ofhydroxylamine hydrochloride to give the appropriately substituted2-aryl-1-hydroxypyrrole-3-carbonitrile represented by the structuralformula VII. The reaction is conducted at an elevated temperature,preferably about 70° C. to 100° C.

Conversion of the 2-phenyl-1-hydroxypyrrole-3-carbonitrile or2-(substituted phenyl)-1-hydroxypyrrole-3-carbonitrile to thecorresponding 4-halo, 5-halo or 4,5-dihalo-2-(substitutedphenyl)-1-hydroxypyrrole-3-carbonitrile, is readily achieved by reactionof the above said 2-phenyl-1-hydroxypyrrole-3-carbonitrile or2-(substituted phenyl)-1-hydroxypyrrole-3-carbonitrile with at least oneequivalent of bromine or a sulfuryl halide, in the presence of a solventsuch as dioxane, tetrahydrofuran, acetic acid or a chlorinatedhydrocarbon solvent. When sulfuryl chloride or sulfuryl bromide is usedthe reaction is generally conducted at temperatures below 40° C.,preferably at about 0° C. to 30° C., but when elemental bromine isemployed, the reaction is usually conducted at about 20° C.-50° C. Otherhalogenating agents that may be employed include sodium hypochlorite,t-butylhypochlorite, N-bromosuccinimide, N-iodosuccinimide and the like.The reactions are illustrated as follows: ##STR7##

Certain of the 5-arylpyrrole-2,3-dicarbonitrile compounds of formula Imay be prepared by reacting the oxime of 2-bromoacetophenone, or asubstituted derivative thereof, with sodium oxalacetate to givephenacyloxalacetate 3-oxime or (substituted phenacyl)oxalacetate3-oxime. The said oxalacetate intermediate is then reacted withhydrochloric acid in an alcohol to give a5-aryl-1-hydroxypyrrole-3-carboxylate represented by structural formulaVIII wherein R₆ is C₁ -C₆ alkyl or C₂ -C₆ cycloalkyl. The resultanthydroxypyrrole intermediate is reacted with methyl iodide and potassiumt-butoxide to give 5-aryl-1-methoxypyrrole-3-carboxylate. Saponificationof the thus- obtained carboxylate gives5-aryl-1-methoxypyrrole-3-carboxylic acid. The thus obtainedmethoxypyrrole-3-carboxylic acid is then reacted with chlorosulfonylisocyanate and dimethylformamide to give the formula I5-aryl-1-methoxypyrrole-2,3-dicarbonitrile, which can be halogenatedusing standard procedures to give other compounds of formula I. Thisreaction scheme is illustrated as follows: ##STR8##

Similarly, the formula III 5-arylpyrrole-3-carbonitrile compounds of thepresent invention may be prepared by the sequential reaction of theabove-mentioned ethyl 5-aryl-1-methoxypyrrole-3-carboxylate with bromineand then saponification to yield2,4-dibromo-5-aryl-1-methoxypyrrole-3-carboxylic acid, which is thenreacted with chlorosulfonyl isocyanate and dimethylformamide to give theformula III 2,4-dibromo-5-aryl-1-methoxypyrrole-3-carbonitrile. Thereactions may be illustrated as follows: ##STR9##

The formula III carbonitrile compounds of the present invention may alsobe prepared from the reaction of a trifluoroacetoacetate with the oximeof a substituted or unsubstituted a-bromoacetophenone in the presence ofsodium hydride to give a 2-(substitutedphenacyl)-4,4,4-trifluoroacetoacetate 2-oxime intermediate. The saidacetoacetate intermediate is reacted with hydrochloric acid in analcohol to form5-aryl-1-hydroxy-2-(trifluoromethyl)pyrrole-3-carboxylate. The(trifluoromethyl)pyrrole-3-carboxylate is reacted with methyl iodide andpotassium tert-butoxide to yield5-aryl-1-methoxy-2-(trifluoromethyl)pyrrole-3-carboxylate. Brominationand saponification of said compound gives a4-bromo-5-aryl-1-methoxy-2-(trifluoromethyl)pyrrole-3-carboxylic acidintermediate which is then reacted with chlorosulfonyl isocyanate anddimethylformamide to give the4-bromo-5-aryl-1-methoxy-2-(trifluoromethyl)pyrrole-3-carbonitrilecompounds of formula III as illustrated below: ##STR10##

Preparation of formula IV 5-aryl-1-methoxypyrrole-2-carbonitrilecompounds can be achieved by reaction of the above mentioned5-aryl-1-methoxypyrrole-3-carboxylic acid, ethyl ester withchlorosulfonyl isocyanate and dimethylformamide to give2-cyano-5-aryl-1-methoxypyrrole-3-carboxylic acid, ethyl ester.Saponification and bromination of the said methoxypyrrole-3-carboxylicacid, ethyl ester intermediate gives the formula IV,3,4-dibromo-5-phenyl-1-methoxypyrrole-2-carbonitrile or3,4-dibromo-5-(substituted phenyl)-1-methoxypyrrole-2-carbonitrile. Thisreaction scheme is illustrated as follows: ##STR11##

Similarly, other formula I N-oxygenated arylpyrroles may be prepared bythe following reactions. ##STR12##

Another method of preparing 3-aryl N-oxygenated pyrroles is thefollowing: ##STR13##

N-oxygenated arylpyrroles can be prepared by reaction of theappropriately substituted formula I N-oxygenated arylpyrrole, wherein Ais hydrogen, and L, M, R, W, X and Y are as described above, with anappropriate alkylating agent and a suitable base, for example, achloromethyl C₁ -C₄ alkyl ether and potassium t-butoxide. This reactionprovides an N-oxygenated arylpyrrole having the same substituents as thestarting material, but in addition is substituted on the oxygen with C₁-C₄ alkoxymethyl. In a similar reaction bromoacetronitrile issubstituted for the chloromethyl C₁ -C₄ alkyl ether and yields theformula I N-oxygenated arylpyrrole with an acetonitrile substituent onthe oxygen. The reactions may be illustrated as follows: ##STR14##wherein L, M, R, W, X and Y are as described for formula I above and Ais (1) C₁ -C₄ alkoxymethyl or (2) CH₂ CN.

Similarly, N-oxygenated arylpyrroles can be prepared by reaction of theappropriately substituted formula I N-oxygenated arylpyrrole, wherein Ais hydrogen, and L, M, R, W, X and Y are as described above, with anappropriate acylating agent and a suitable base, for example, a C₁ -C₆acid chloride and potassium t-butoxide. This reaction provides anN-oxygenated arylpyrrole having the same substituents as the startingmaterial, but in addition is substituted on the oxygen with C₁ -C₆alkanoyl. The reaction may be illustrated as follows: ##STR15##

An intermediate useful in the preparation of N-oxygenated arylpyrroleshas the structural formula IX: ##STR16## wherein X is H or CF₃ ;

L is H, F, Cl or Br;

M and R are each independently H, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₃alkylthio, C₁ -C₃ alkylsulfinyl, C₁ -C₃ alkylsulfonyl, cyano, F, Cl, Br,I, nitro, CF₃, R₁ CF₂, R₂ CO or NR₃ R₄ ;

and when M and R are on adjacent positions and taken with the carbonatoms to which they are attached they may form a ring in which MRrepresents the structure: ##STR17## Z is S(O)_(n) or O; R₁ is H, F, CHF₂CHFCl or CF₃ ;

R₂ is C₁ -C₃ alkyl, C₁ -C₃ alkoxy or NR₃ R₄ ;

R₃ is H or C₁ -C₃ alkyl;

R₄ is H, C₁ -C₃ alkyl or R₅ CO;

R₅ is H or C₁ -C₃ alkyl; and

n is an integer of 0, 1 or 2; and

R₆ is hydrogen, C₁ -C₆ alkyl or C₃ -C₆ cycloalkyl.

The preparation of formula IX compounds is shown in previousillustrations, excepting when R₆ is hydrogen.

Hydrolysis of a formula IX compound when R₆ is not hydrogen yieldsanother formula IX compound having the same structure except that R₆ isnow hydrogen.

The N-oxygenated arylpyrroles of the present invention are effective forcontrolling insects, acarina and nematodes. These compounds are alsoeffective for protecting growing or harvested crops from attack by theabove-said pests.

In practice generally about 10 ppm to 10,000 ppm and preferably 100 ppmto about 5,000 ppm of a formula I N-oxygenated arylpyrrole, dispersed inwater, or another inexpensive liquid carrier, is effective when appliedto the plants, the crops or the soil in which said crops are growing toprotect said crops from attack by insects, acarina and/or nematodes.These compounds are also useful for protecting turf grass from attack bypests such as grubs, chinch bugs and the like.

The formula I N-oxygenated arylpyrroles of this invention are alsoeffective for controlling insects, nematodes and acarina, when appliedto the foliage of plants and/or to the soil or water in which saidplants are growing in sufficient amount to provide a rate of from about0.100 kg/ha to 4.0 kg/ha of active ingredient.

While the N-oxygenated arylpyrroles of this invention are effective forcontrolling insects, nematodes and acarina when employed alone, they mayalso be used in combination with other biological chemicals, includingother insecticides, nematicides and acaricides. For example, theN-oxygenated arylpyrroles of this invention may be used effectively inconjunction or combination with phosphates, carbamates, pyrethroids,formamidines, chlorinated hydrocarbons, halobenzoylureas and the like.

Advantageously, the above-said N-oxygenated arylpyrroles may beformulated into dry compacted granules, flowable compositions, granularformulations, wettable powders, dusts, dust concentrates, microemulsionsand the like, all of which lend themselves to soil, water and/or foliageapplication and provide the requisite plant protection. Suchformulations include the compounds of the invention admixed with inert,pharmacologically-acceptable solid or liquid diluents.

For example, wettable powders, dusts and dust concentrate formulationsof the invention can be prepared by grinding together about 3% to 20%,by weight, of the formula I N-oxygenated arylpyrrole compound, withabout 3% to 20% by weight of a solid anionic surfactant. One suitableanionic surfactant is a dioctyl ester of sodium sulfosuccinic acid,specifically Aerosol OTB® surfactant marketed by the American CyanamidCompany. About 60% to 94%, by weight, of an inert solid diluent, such asmontmorillonite, attapulgite, chalk, talc, kaolin, diatomaceous earth,limestone, silicates or the like also is used in such formulations.

Compacted granules especially useful for soil or water application canbe prepared by grinding together in about equal parts, usually about 3to 20 parts of the N-oxygenated arylpyrrole and a solid surfactant, withabout 60 to 94 parts of gypsum. Thereafter, the mixture is compactedinto small granular particles, about 24/48 mesh or larger.

Other suitable solid surfactants useful in the present formulationsinclude not only the anionic dioctyl ester of sodium sulfosuccinic acidbut also nonionic block copolymers of ethylene oxide and propyleneoxide. Such block copolymers are marketed by BASF Wyandotte Corporationas Pluronic 10R8®, 17R8®, 25R8®, F38®, F68®, F77® or F87®, and areespecially effective for the preparation of compacted granules.

In addition to the powders and concentrate formulations describedhereinabove, wettable powders and flowables may be used because they maybe dispersed in water. Preferably, such flowables will be applied at thelocus with the aqueous compositions being sprayed on the foliage ofplants to be protected. These sprays also may be applied to the breedingground, food supply or habitat of the insects and acarina sought to becontrolled.

Where solid formulations of the compounds of this invention are to beused in combination treatments with other pesticidal agents, theformulations can be applied as an admixture of the components or may beapplied sequentially.

Similarly, liquid formulations of the N-oxygenated arylpyrrole incombination with other pesticidal agents may be tank mixed or may beapplied separately, sequentially, as liquid sprays. Liquid sprayformulations of the compounds of the invention should contain about0.001% to 0.1% by weight of the active N-oxygenated arylpyrrole.

In order to facilitate a further understanding of the invention, thefollowing examples are presented primarily for the purpose ofillustrating more specific details thereof. The invention is not to bedeemed limited thereby except as defined in the claims.

EXAMPLE 1 Preparation of starting material,3-(p-Chlorobenzoyl)-3-cyano-1-propionaldehyde, dimethyl acetal ##STR18##

To a stirred slurry of sodium hydride (60% in mineral oil, 4.4 g, 0.11mol) in anhydrous ethylene glycol dimethyl ether is added, dropwise,cyanopropionaldehyde dimethyl acetal (12.9 g, 0.1 mol). The resultingmixture is heated at 50° C. for 30 minutes, treated with a solution ofp-chlorobenzoate methyl ester (17.1 g, 0.1 mol) in ethylene glycoldimethyl ether, heated at reflux temperature 12 hours, cooled to roomtemperature, quenched with isopropanol and concentrated in vacuo to givea liquid. The liquid is diluted with water, acidified with dilutehydrochloric acid and extracted with ether. The combined ether extractsare washed sequentially with water, saturated sodium bicarbonatesolution, water and brine, dried over anhydrous sodium sulfate andconcentrated in vacuo to give a liquid. The liquid is chromatographedusing silica gel, methylene chloride and 3% ethyl acetate in methylenechloride as eluent to give the title compound as a yellow liquid (14.4g, 54%), identified by IR and NMR spectral analysis.

Following the procedure described in Example 1, but using theappropriately substituted methyl phenylbenzoate, the compounds shownbelow are obtained.

    ______________________________________                                         ##STR19##                                                                    L              M        R                                                     ______________________________________                                        H              4-Cl     H                                                     H              3-Cl     4-Cl                                                  H              .sup.  4-CF.sub.3                                                                      H                                                     ______________________________________                                    

EXAMPLE 2 Preparation of2-(p-Chlorophenyl)-1-hydroxypyrrole-3-carbonitrile ##STR20##

A stirred mixture of 3-(p-chlorobenzoyl)-3-cyano-1-propionaldehydedimethyl acetal (10.0 g, 0.0373 mol) and hydroxylamine hydrochloride(3.89 g, 0.056 mol) in ethanol is heated to reflux temperature for onehour, cooled to room temperature and concentrated in vacuo to give aliquid. The liquid is dissolved in ether, washed sequentially with waterand brine, dried over anhydrous sodium sulfate and concentrated in vacuoto yield a brown gum. The gum is chromatographed using silica gel,methylene chloride and 3% ethyl acetate in methylene chloride as eluentto give a brown solid. Recrystallization from methylene chloride/hexanesgives the title compound as a pale brown solid (6.0 g, 74%), mp148.5°-150° C.

Following the procedure described in Example 2, but using theappropriately substituted 3-(benzoyl)-3-cyano-1-propionaldehyde dimethylacetal, the compounds shown below are obtained.

    ______________________________________                                         ##STR21##                                                                    L      M              R      mp °C.                                    ______________________________________                                        H      4-Cl           H      148.5-150.0                                      H      3-Cl           4-Cl   207.0-208.0                                      H      .sup.  4-CF.sub.3                                                                            H      124.0-126.5                                      ______________________________________                                    

EXAMPLE 3 Preparation of4,5-Dibromo-2-(p-chlorophenyl)-1-hydroxypyrrole-3-carbonitrile ##STR22##

Bromine (2.3 g, 0.0144 mol) is added dropwise to a stirred solution of2-(p-chlorophenyl)-1-hydroxypyrrole-3-carbonitrile (1.5 g, 0.007 mol) indry p-dioxane at room temperature. After one hour, the reaction mixtureis diluted with water and extracted with ether. The combined etherextracts are washed sequentially with water, saturated sodiumbicarbonate solution, water and brine, dried over anhydrous sodiumsulfate and concentrated in vacuo to give a solid. Recrystallization ofthe solid from ethyl acetate/hexanes gives the title compound as a whitepowder (1.98 g, 75%), mp 208°-209° C.

EXAMPLE 4 Preparation of4,5-Dichloro-2-(p-chlorophenyl)-1-hydroxypyrrole-3-carbonitrile##STR23##

Sulfuryl chloride (1.95 g, 0.014 mol) is added dropwise to a stirredsolution of 2-(p-chlorophenyl)-1-hydroxypyrrole-3-carbonitrile (1.5 g,0.007 mol) in glacial acetic acid, the temperature rises to 45° C. and ayellow solid precipitates out. After 21/2 hours the reaction mixture isdiluted with water and extracted with ethyl acetate. The combined ethylacetate extracts are washed sequentially with water, saturated sodiumbicarbonate solution, water and brine, dried over anhydrous sodiumsulfate and concentrated in vacuo to yield a brown solid. The solid ischromatographed using silica gel, methylene chloride and 3% ethylacetate in methylene chloride as eluent to give the title compound as abrown powder (0.5 g, 25%), mp 156.5° C.

Following the procedure of either Example 3 or 4, but using theappropriately substituted 2-phenylpyrrole yields the followingcompounds.

    ______________________________________                                         ##STR24##                                                                    A    L     M        R    Y    W    X       mp °C.                      ______________________________________                                        H    H     4-Cl     H    Br   CN   Br      208.0-209.0                        H    H     3-Cl     4-Cl Br   CN   Br      222.5-223.0                        H    H     .sup.  4-CF.sub.3                                                                      H    Br   CN   Br      217.0-217.5                        CH.sub.3                                                                           H     4-Cl     H    Br   Br   COOC.sub.2 H.sub.5                                                                     98.0-101.0                        CH.sub.3                                                                           H     4-Cl     H    CF.sub.3                                                                           Br   COOC.sub.2 H.sub.5                                                                    47.0-50.0                          H    H     4-Cl     H    Cl   CN   Cl      156.5                              H    H     3-Cl     4-Cl Cl   CN   Cl      197.0-197.5                        ______________________________________                                    

EXAMPLE 5 Preparation of2-(p-Chlorophenyl)-1-methoxypyrrole-3-carbonitrile ##STR25##

To a stirred solution of2-(p-chlorophenyl)-1-hydroxypyrrole-3-carbonitrile (2.88 g, 0.0132 mol)and anhydrous tetrahydrofuran is added potassium tert-butoxide (1.55 g,0.0138 mol). After 30 minutes, methyl iodide (2.06 g, 0.9 mL, 0.0145mol) is added and the resulting slurry is stirred at room temperaturefor 3 hours, diluted with water and extracted with ether. The combinedether extracts are washed sequentially with water and brine, dried overanhydrous magnesium sulfate and concentrated in vacuo to yield a solid.Crystallization of the solid from ether/hexanes gives the title compoundas a brown solid (2.35 g, 77%), mp 105°-106° C.

Following the procedure described in Example 5, but using theappropriately substituted 2-phenyl-1-hydroxypyrrole-3-carbonitrile andthe appropriate alkylating or acylating agent, the compounds shown beloware obtained.

    ______________________________________                                         ##STR26##                                                                    A         L      M        R    X    Y    mp °C.                        ______________________________________                                        CH.sub.2 OC.sub.2 H.sub.5                                                               H      4-Cl     H    Cl   Cl   75.0-76.5                            CH.sub.2 OC.sub.2 H.sub.5                                                               H      4-Cl     H    Br   Br   75.0-76.0                            CH.sub.2 CCH                                                                            H      4-Cl     H    Cl   Cl   140.5-142.0                           ##STR27##                                                                              H      4-Cl     H    Br   Br   176.5-177.5                          CH.sub.2 CN                                                                             H      4-Cl     H    Cl   Cl   128.0-130.0                           ##STR28##                                                                              H      4-Cl     H    Br   Br   129.5-131.0                          CH.sub.3  H      3-Cl     4-Cl Cl   Cl   152.0-156.0                           ##STR29##                                                                              H      4-Cl     H    Br   Br   131.5-132.0                          CH.sub.2 CN                                                                             H      3-Cl     4-Cl Cl   Cl   170.0-182.0                           ##STR30##                                                                              H      4-Cl     H    Br   Br   148.5-149.5                          CH.sub.2 CN                                                                             H      4-Cl     H    Br   Br   144.0-145.5                          CH.sub.2 CCH                                                                            H      4-Cl     H    Br   Br   145.0-147.0                           ##STR31##                                                                              H      4-Cl     H    Br   Br   110.0-112.0                          CH.sub.3  H      3-Cl     4-Cl Br   Br   183.0-184.0                          CH.sub.2 OC.sub.2 H.sub.5                                                               H      3-Cl     4-Cl Br   Br   91.5-92.5                            CH.sub.3  H      .sup.  4-CF.sub.3                                                                      H    Br   Br   204.5-207.5                          CH.sub.3  H      4-Cl     H    Cl   Cl   147.0-149.0                          ______________________________________                                    

EXAMPLE 6 Preparation of4,5-Dibromo-2-(p-chlorophenyl)-1-methoxypyrrole-3-carbonitrile ##STR32##

Bromine (2.16 g, 0.7 mL, 0.0135 mol) is added dropwise to a stirredsolution of 2-(p-chlorophenyl)-1-methoxypyrrole-3-carbonitrile (1.5 g,0.00645 mol) in anhydrous p-dioxane. After 3 hours, the reaction mixtureis diluted with water and filtered. The solids are washed with water anddried to yield the title compound as a white solid (2.48 g, 98%), mp190°-190.5° C.

EXAMPLE 7 Preparation of (p-Chlorophenacyl)oxalacetic acid, diethylester, 3-oxime ##STR33##

A solution of 2-bromo-4'-chloroacetophenone, oxime (24.9 g, 0.1 mol) inethylene glycol dimethyl ether is added slowly to a 50° C. stirredsolution of sodium diethyl oxalacetate (21.0 g, 0.1 mol) in ethyleneglycol dimethyl ether. After the addition, the reaction mixture isheated at reflux temperature for 1 hour, cooled to room temperature andconcentrated in vacuo to give a liquid. The liquid is dissolved in etherand washed sequentially with water and brine, dried over anhydroussodium sulfate and concentrated in vacuo to yield a solid.Recrystallization from ether/hexanes gives the title compound as a whitesolid (18.0 g, 51%), mp 119°-120° C.

Following the procedure described in Example 7, but using theappropriately substituted 2-bromoacetophenone, oxime, the compoundsshown below are obtained.

    ______________________________________                                         ##STR34##                                                                    L       M            R      mp °C.                                     ______________________________________                                        H       4-Cl         H      119.0-120.0                                       H       3-Cl         4-Cl    99.5-104.0                                       ______________________________________                                    

EXAMPLE 6 Preparation of5-(p-Chlorophenyl)-1-hydroxypyrrole-3-carboxylic acid, diethyl ester##STR35##

(p-Chlorophenyl)oxalacetic acid, diethyl ester, 3-oxime (26.0 g, 0.073mol) in ethanol, saturated with HCl gas, is heated at reflux temperaturefor 90 minutes, cooled to room temperature, diluted with water andextracted with ether. The combined ether extracts are washedsequentially with water and brine, dried over anhydrous sodium sulfateand concentrated in vacuo to yield a gum. The gum is chromatographedusing silica gel, methylene chloride and eluted sequentially with 1%ethyl acetate in methylene chloride and 3% ethyl acetate in methylenechloride to yield 2 products. The less polar fractions give5-(p-chlorophenyl)-1-hydroxypyrrole-2,3-dicarboxylic acid, diethyl ester(7.3 g, 30%), mp 82°-84° C. Recrystallization from methylenechloride/hexanes, of the more polar fractions, gives the title compoundas a white solid (10.5 g, 54%), mp 111°-116° C.

Following the procedures described in Example 8, but using theappropriately substituted phenacyloxalacetic acid, diethyl ester,3-oxime, the compounds shown below are obtained.

    ______________________________________                                         ##STR36##                                                                    L       M            R      mp °C.                                     ______________________________________                                        H       4-Cl         H      111.0-116.0                                       H       3-Cl         4-Cl   146.0-148.0                                       ______________________________________                                    

EXAMPLE 9 Preparation of5-(p-Chlorophenyl)-1-methoxypyrrole-3-carboxylic acid, ethyl ester##STR37##

Potassium tert-butoxide (4.32 g, 0.0385 mol) is added portionwise to a0° C. solution of ethyl5-(p-chlorophenyl)-1-hydroxypyrrole-3-carboxylate (9.3 g, 0.035 mol) inanhydrous tetrahydrofuran. Methyl iodide (5.46 g, 0.0385 mol) is thenadded slowly to the solution at room temperature. The reaction mixtureis stirred for 3 hours, diluted with water and extracted with ether. Thecombined ether extracts are washed sequentially with water and brine,dried over anhydrous sodium sulfate and concentrated in vacuo to give asolid. Crystallization from hexanes gives the title compound as a whitecrystalline solid (9.25 g, 94%), mp 65°-66° C.

Following the procedure described in Example 9, but using theappropriately substituted 2-phenyl-1-hydroxypyrrole, the compounds shownbelow are obtained.

    ______________________________________                                         ##STR38##                                                                    Y           L     M          R    mp °C.                               ______________________________________                                        H           H     4-Cl       H    65.0-66.0                                   H           H     3-Cl       4-Cl 69.5-72.5                                   COOC.sub.2 H.sub.5                                                                        H     4-Cl       H    72.0-73.0                                   CF.sub.3    H     4-Cl       H    68.0-71.0                                   ______________________________________                                    

EXAMPLE 10 Preparation of5-(p-Chlorophenyl)-1-methoxypyrrole-3-carboxylic acid ##STR39##

Sodium hydroxide (50%, 2.75 g, 0.0343 mol) in water is added to astirred solution of ethyl5-(p-chlorophenyl)-1-methoxypyrrole-2-carboxylate (8.0 g, 0.0286 mol) inethanol. The reaction mixture is heated at reflux temperature for 2hours, cooled to room temperature, diluted with water and extracted withether. The aqueous layer is acidified with 10% hydrochloric acid andextracted with ether. The combined ether extracts are washedsequentially with water and brine, dried over anhydrous sodium sulfateand concentrated in vacuo to yield a solid which upon trituration withboiling hexanes gives the title compound as a white crystalline solid(7.0 g, 97%), mp 189°-191° C.

Following the procedure described in Example 10, but using theappropriately substituted 2-phenyl-1-methoxypyrrole, the compounds shownbelow are obtained.

    ______________________________________                                         ##STR40##                                                                    L     M         R      Y       X    mp °C.                             ______________________________________                                        H     4-Cl      H      H       H    189.0-191.0                               H     3-Cl      4-Cl   H       CN   221.5-226.5                               H     4-Cl      H      Br      CF.sub.3                                                                           215.0-217.0                               ______________________________________                                    

EXAMPLE 11 Preparation of5-(p-Chlorophenyl)-1-methoxypyrrole-2,3-dicarbonitrile ##STR41##

Chlorosulfonyl isocyanate (8.1 g, 0.0572 mol) is added dropwise to a 50°C. stirred mixture of 5-(p-chlorophenyl)-1-methoxypyrrole-3-carboxylicacid (6.0 g, 0.0238 mol) in acetronitrile and dimethylformamide. Thereaction mixture is stirred at room temperature for 20 hours, cooled to0° C., treated with dimethylformamide (9.2 mL), heated to 50° C. for 1hour, cooled to room temperature for 3 hours, diluted with water andextracted with chloroform. The combined chloroform extracts are washedsequentially with water, saturated sodium bicarbonate solution, waterand brine, dried over anhydrous sodium sulfate and concentrated in vacuoto give a gum. The gum is chromatographed using silica gel, andmethylene chloride as eluent to give 2 products as a mixture.Crystallization from chloroform gives2-(p-chlorophenyl)-1-methoxypyrrole-3,4-dicarbonitrile (1.1 g, 18%), asa yellow solid, mp 193°-194° C. The filtrate from the abovecrystallization is chromatographed using silica gel, and 30% ethylacetate in heptane as eluent to give the title compound as a yellowsolid (0.93 g, 15%), mp 126°-127° C.

Following the procedure described in Example 11, but using theappropriately substituted 2-phenyl-1-methoxypyrrole, the compounds shownbelow are obtained.

    ______________________________________                                         ##STR42##                                                                    L    M       R       X     Y    J       mp °C.                         ______________________________________                                        H    4-Cl    H       CN    H    CN      126.0-127.0                           H    3-Cl    4-Cl    CN    H    COOC.sub.2 H.sub.5                                                                    128.0-130.5                           H    4-Cl    H       CF.sub.3                                                                            Br   CN      138.0-150.0                           ______________________________________                                    

EXAMPLE 12 Preparation of4-Bromo-5-(p-chlorophenyl)-1-methoxypyrrole-2,3-dicarbonitrile ##STR43##

Bromine (0.341 g, 0.00213 mol) is added to a stirred mixture of5-(p-chlorophenyl)-1-methoxypyrrole-2,3-dicarbonitrile (0.5 g, 0.00193mol) and sodium acetate (0.318 g, 0.00388 mol) in acetic acid. Thereaction mixture is heated at 95°-100° C. overnight, cooled to roomtemperature, diluted with water and extracted with ethyl acetate. Thecombined ethyl acetate extracts are washed sequentially with water,saturated sodium bicarbonate solution, aqueous sodium metabisulfitesolution, water and brine, dried over anhydrous magnesium sulfate andconcentrated in vacuo to yield a solid that is crystallized from ethylacetate/hexanes to give the title compound as a yellow solid (0.406 g,62%), mp 166.5°-167° C.

Following the procedure described in Example 12, but using theappropriately substituted 2-phenyl-1-methoxypyrrole, the compounds shownbelow are obtained.

    ______________________________________                                         ##STR44##                                                                    L     M         R     W        X    mp °C.                             ______________________________________                                        H     4-Cl      H     Br       CN   166.5-167.0                               H     4-Cl      H     CN       Br   211.0-212.0                               ______________________________________                                    

EXAMPLE 13 Preparation of3,4-Dibromo-5-(3,4-dichlorophenyl)-1-methoxypyrrole-2-carbonitrile##STR45##

Bromine (1.13 g, 0.0071 mol) is added to a stirred solution of2-cyano-5-(3,4-dichlorophenyl)-1-methoxypyrrole-3-carboxylic acid (1.0g, 0.0032 mol) in glacial acetic acid. The reaction mixture is heated atreflux temperature for 2.5 hours, cooled to room temperature, dilutedwith water and extracted with ether. The combined ether extracts arewashed sequentially with water, saturated sodium bicarbonate solution,water and brine, dried over anhydrous magnesium sulfate, andconcentrated in vacuo to give a solid. Recrystallization of the solidfrom ether/hexanes yields the title compound as a white solid (0.46 g,34%), mp 145°-150° C.

EXAMPLE 14 Preparation of2,4-Dibromo-5-(p-chlorophenyl)-1-methoxypyrrole-3-carbonitrile ##STR46##

Chlorosulfonyl isocyanate (1.66 g, 0.0117 mol) is added to a 5° C.stirred solution of2,4-dibromo-5-(p-chlorophenyl)-1-methoxypyrrole-3-carboxylic acid (2.0g, 0.0049 mol) in acetronitrile. The solution is heated to 45°-50° C.for 2 hours, acetronitrile is added, cooled to 5° C. anddimethylformamide (1.9 mL, 0.0244 mol) is added. The reaction mixture isstirred at room temperature for 3 hours, diluted with water andextracted with chloroform. The combined chloroform extracts are washedsequentially with water and saturated sodium bicarbonate solution, driedover anhydrous magnesium sulfate and concentrated in vacuo to give ayellow solid. Chromatography using silica gel, methylene chloride and 3%ethyl acetate in methylene chloride as eluent yields the title compoundas an off-white solid (0.23 g, 12%), mp 195°-197° C.

EXAMPLE 15 Preparation of 2-(p-Chlorophenacyl)-4,4,4-trifluoroaceticacid, ethyl ester, 2-oxime, (E)- and (Z)- ##STR47##

Under nitrogen, sodium hydride (60% in mineral oil, 3.04 g, 0.076 mol)is added portionwise to anhydrous ethylene glycol dimethyl ether and themixture is heated to 40°-45° C. Ethyl trifluoroacetoacetate (14.0 g,0.076 mol) is added dropwise over 30 minutes. Once the addition iscomplete, the reaction mixture is heated at 45°-50° C. for 1 hour andthen a mixture of 2-bromo-4'-chloroacetophenone, oxime, (E)- (18 g,0.0724 mol) in ethylene glycol dimethyl ether is added dropwise. Theresulting slurry is heated at reflux temperature for 1 hour, cooled toroom temperature and the solids are filtered off. The filtrate isconcentrated in vacuo to give a solid residue which is dissolved inether. The ether solution is washed sequentially with water and brine,dried over anhydrous magnesium sulfate and concentrated in vacuo to givea solid which is crystallized from ether/hexanes to yield the titlecompound as a white solid (17 g, 67%), mp 154°-154.5 ° C.

EXAMPLE 16 Preparation of5-(p-Chlorophenyl)-1-hydroxy-2-(trifluoromethyl)pyrrole-3-carboxylicacid, ethyl ester ##STR48##

A stirred mixture of 2-(p-chlorophenacyl)-4,4,4-trifluoroacetic acid,ethyl ester, 2-oxime, (E)- and (Z)- (7.03 g, 0.02 mol) and ethanol,saturated with HCl gas, is heated at reflux temperature for 90 minutes.Excess HCl gas is removed by bubbling nitrogen through the reactionmixture at room temperature. The solvent is evaporated in vacuo and theresidual solid is chromatographed using silica gel, methylene chlorideand 3% ethyl acetate in methylene chloride as eluent to yield a solid.Crystallization from ethyl acetate/hexanes gives the title compound as awhite solid (3.1 g, 46%), mp 161°-161.5° C.

EXAMPLE 17 Preparation of5-(p-Chlorophenyl)-1-methoxy-4-nitro-2-(trifluoromethyl)pyrrole-3-carboxylicacid, ethyl ester ##STR49##

Fuming nitric acid (90%, 0.75 mL, 0.0167 mol) is added dropwise to a 5°C. solution of5-(p-chlorophenyl)-1-methoxy-2-(trifluoromethyl)pyrrole-3-carboxylicacid, ethyl ester (3.27 g, 0.0094 mol) in acetic anhydride. Afterstirring at room temperature overnight, the reaction mixture is dilutedwith water and extracted with ether. The combined ether extracts arewashed sequentially with water and brine, dried over anhydrous magnesiumsulfate and concentrated in vacuo to give a thick yellow liquid.Chromatography using silica gel, methylene chloride and 2% ethyl acetatein methylene chloride as eluent gives a solid. Recrystallization fromhexanes gives the title compound as a white solid (2.02 g, 55%), mp90°-92° C.

Following the procedure described in Example 17, but using theappropriately substituted 2-phenyl-1-methoxypyrrole, the compounds shownbelow are obtained.

    ______________________________________                                         ##STR50##                                                                    Y         W            X      mp °C.                                   ______________________________________                                        COOC.sub.2 H.sub.5                                                                      NO.sub.2     CF.sub.3                                                                             90-92                                           H         CN           NO.sub.2                                                                             196-200                                         NO.sub.2  CN           H      175-184                                         ______________________________________                                    

EXAMPLE 18 Insecticide and acaricide evaluations

The following tests show the efficacy of the compounds as insecticidesand acaricides. All tests are performed using technical materials andkept at 27° C. The test concentrations are in terms of activeingredient.

Spodoptera eridania, 3rd instar larvae, southern armyworm

A sieva lima bean leaf expanded to 7 to 8 cm in length is dipped in thetest suspension with agitation for 3 seconds and placed in a hood todry. The leaf is then placed in a 100×10 mm petri dish containing a dampfilter paper on the bottom and 10 3rd instar caterpillars. The dish ismaintained for 5 days before observations are made of mortality, reducedfeeding, or any interference with normal moulting.

Spodoptera eridania, 7-day residual

The plants treated in the above test are maintained under high intensitylamps in the greenhouse for 7 days. These lamps duplicate the effects ofa bright sunny day and are kept on for 14 hour day length. After 7 days,the foliage is sampled and assayed as in the above-said test.

Aphis fabae, mixed instar, bean aphid

Pots containing single nasturtium plants (Tropaeolum sp.) about 5 cmtall are infested with about 100 to 200 aphids one day before the test.Each pot is sprayed with the test formulation for 2 revolutions of a 4rpm turntable in a hood, using a #154 DeVilbiss atomizer. The spray tipis held about 15 cm from the plant and the spray directed so as to givecomplete coverage of the plants and the aphids. The sprayed pots are seton their sides on white enamel trays and held for 2 days, followingwhich mortality estimates are made.

Tetranychus urticae (P-resistant strain), 2-spotted spider mite

Sieva lima bean plants with primary leaves expanded to 7 to 8 cm areselected and cut back to one plant per pot. A small piece is cut from aleaf taken from the main colony and placed on each leaf of the testplants. This is done about 2 hours before treatment to allow the mitesto move over to the test plant and to lay eggs. The size of the cutpiece is varired to obtain about 100 mites per leaf. At the time of thetreatment, the piece of leaf used to transfer the mites is removed anddiscarded. The mite-infested plants are dipped in the test formulationfor 3 seconds with agitation and set in the hood to dry. Plant are keptfor 2 days before estimates of adult kill are made using the first leaf.The second leaf is kept on the plant for another 5 days beforeobservations are made of the kill of eggs and/or newly emerged nymphs.

Diabrotic undecimpunctata howardi, 3rd instar southern corn rootworm.

One cc of fine talc is placed in a 30 mL wide-mouth screw-top glass jar.One mL of the appropriate acetone suspension is pipetted onto the talcso as to provide 1.25 and 0.25 mg of active ingredient per jar. The jarsare set under a gentle air flow until the acetone is evaporated. Thedried talc is loosened, 1 cc of millet seed is added to serve as foodfor the insects and 25 mL of moist soil is added to each jar. The jar iscapped and the contents thoroughly mixed on a Vortex Mixer. Followingthis, 10 3rd instar rootworms are added to each jar and the jars areloosely capped to allow air exchange for the larvae. The treatments areheld for 6 days before mortality counts are made. Missing larvae arepresumed dead, since they decompose rapidly and can not be found. Theconcentrations used in this test correspond approximately to 50 and 10kg/ha, respectively.

    ______________________________________                                        Rating Scale:                                                                 ______________________________________                                        0 = no effect      5 = 56 to 65% kill                                         1 = 10 to 25% kill 6 = 66 to 75% kill                                         2 = 26 to 35% kill 7 = 76 to 85% kill                                         3 = 36 to 45% kill 8 = 86 to 99% kill                                         4 = 46 to 55% kill 9 = 100% kill                                                                 R = reduced feeding                                        ______________________________________                                    

The data obtained for the above-described evaluations are reported inTable I.

                                      TABLE I                                     __________________________________________________________________________    Insecticide And Acaricide Evaluations                                                      BEAN            P. RES                                                        APHIDS                                                                             Southern Armyworm                                                                        MITES                                                                              SCRW.sup.1                                               (ppm)                                                                              (ppm)                                                                             (ppm)                                                                             7  (ppm)                                                                              (kg/ha)                                     Compound     100  1000                                                                              100 days                                                                             300  50                                          __________________________________________________________________________    4,5-Dibromo-2-( -p-chloro-                                                                 0    9   9   9  0    0                                           phenyl)-1-hydroxypyrrole-                                                     3-carbonitrile                                                                4,5-Dichloro-2-( -p-chloro-                                                                0    9   9   9  0    0                                           phenyl)-1-hydroxypyrrole-                                                     3-carbonitrile                                                                4,5-Dibromo-2-( -p-chloro-                                                                 0    9   9   9  5    0                                           phenyl)-1-methoxypyrrole-                                                     3-carbonitrile                                                                4,5-Dibromo-2-( -p-chloro-                                                                 0    9   9   9  0    0                                           phenyl)-1-(ethoxymethoxy)-                                                    pyrrole-3-carbonitrile                                                        4,5-Dibromo-2-( -p-chloro-                                                                 0    9   8   0  0    0                                           phenyl)-1-hydroxypyrrole-                                                     3-carbonitrile, dimethyl                                                      carbamate (ester)                                                             4,5-Dibromo-2-( -p-chloro-                                                                 0    9   9   9  0    0                                           phenyl)-1-hydroxypyrrole-                                                     3-carbonitrile, acetate                                                       (ester)                                                                       2-( -p-Chlorophenyl)-1                                                                     5    9   0   7  0    0                                           methoxy-5-nitropyrrole-                                                       3-carbonitrile                                                                2-( -p-Chlorophenyl)-1-                                                                    0    9   3   9  0    0                                           methoxy-4-nitropyrrole-                                                       3-carbonitrile                                                                2-( -p-Chlorophenyl)-1-                                                                    0    9   0   0  0    0                                           methoxypyrrole-3,4-                                                           dicarbonitrile                                                                2-Bromo-5-( -p-chloro-                                                                     0    9   5   9  0    0                                           phenyl)-1-methoxy-                                                            pyrrole-3,4-dicarbo-                                                          nitrile                                                                       4,5-Dichloro-2-( -p-chloro-                                                                0    9   9   9  0    0                                           phenyl)-1-methoxypyrrole-                                                     3-carbonitrile                                                                4-Bromo-5-( -p-chloro-                                                                     0    9   0   0  0    0                                           phenyl)-1-methoxy-2-                                                          (trifluoromethyl)-                                                            pyrrole-3-carbonitrile                                                        5-( -p-Chlorophenyl)-1-                                                                    0    9   9   9  0    0                                           methoxypyrrole-2,3-                                                           dicarbonitrile                                                                4-Bromo-5-( -p-chloro-                                                                     0    9   9   9  0    0                                           phenyl)-1-methoxy-                                                            pyrrole-2,3-dicarbo-                                                          nitrile                                                                       3,3-Dimethylbutyric acid,                                                                  0    9   9   9  0    0                                           2,3-dibromo-5-( -p-chloro-                                                    phenyl)-4-cyanopyrrol-1-                                                      yl ester                                                                      Pivalic acid, 2,3-di-                                                                      9    9   9   9  0    0                                           bromo-5-( -p-chlorophenyl)-                                                   4-cyanopyrrol-1-yl ester                                                      4,5-Dibromo-2-( -p-chloro-                                                                 0    9   9   9  9    0                                           phenyl)-1-(cyanomethoxy)-                                                     pyrrole-3-carbonitrile                                                        4,5-Dibromo-2-( -p-chloro-                                                                 0    9   9   9  0    0                                           phenyl)-1-(2-propynyloxy)-                                                    pyrrole-3-carbonitrile                                                        4,5-Dibromo-2-( -p-chloro-                                                                 0    9   9   9  0    0                                           phenyl)-1-(1-methoxy                                                          ethoxy)pyrrole-3-carbo-                                                       nitrile                                                                       4,5-Dibromo-2-(3,4-                                                                        0    9   0   9  0    0                                           dichlorophenyl)-1-                                                            hydroxypyrrole-3-                                                             carbonitrile                                                                  4,5-Dibromo-2-(3,4-                                                                        0    9   9   9  0    0                                           dichlorophenyl)-1-                                                            methoxypyrrole-3-                                                             carbonitrile                                                                  4,5-Dibromo-2-(3,4-                                                                        0    9   9   9  0    0                                           dichlorophenyl)-1-                                                            (ethoxymethoxy)-                                                              pyrrole-3-carbonitrile                                                        4,5-Dichloro-2-                                                                            0    9   9   9  0    0                                           ( -p-chlorophenyl)-1-                                                         (ethoxymethoxy)-                                                              pyrrole-3-carbonitrile                                                        4,5-Dichloro-2-( -p-chloro-                                                                0    9   9   9  0    5                                           phenyl)-1-(2-propynyloxy)-                                                    pyrrole-3-carbonitrile                                                        4,5-Dichloro-2-( -p-chloro-                                                                0    9   9   9  0    0                                           phenyl)-1-(cyanomethoxy)-                                                     pyrrole-3-carbonitrile                                                        4,5-Dichloro-2-(3,4-                                                                       0    9   9   9  0    0                                           dichlorophenyl)-1-                                                            methoxypyrrole-3-                                                             carbonitrile                                                                  4,5-Dichloro-2-(3,4-                                                                       0    9   9   9  9    0                                           dichlorophenyl)-1-                                                            hydroxypyrrole-3-                                                             carbonitrile                                                                  4,5-Dichloro-1-                                                                            9    9   9   9  0    9                                           (cyanomethoxy)-2-                                                             (3,4-dichlorophenyl)-                                                         pyrrole-3-carbonitrile                                                        2,4-Dibromo-5-( -p-chloro-                                                                 7    9   9   0  9    5                                           phenyl)-1-methoxy-                                                            pyrrole-3-carbonitrile                                                        1-(Benzyloxy)-4,5-                                                                         --   --  9   0  --   --                                          dichloro-2-( -p-chloro-                                                       phenyl)pyrrole-3-                                                             carbonitrile                                                                  3,4-Dibromo-5-(3,4-                                                                        0    9   9   9  0    0                                           dichlorophenyl)-1-                                                            methoxypyrrole-2-                                                             carbonitrile                                                                  4,5-Dibromo-1-hydroxy-                                                                     0    9   9   0  0    4                                           2-(alpha,alpha,alpha-                                                         trifluoro-p-tolyl)-                                                           pyrrole-3-carbonitrile                                                        4,5-Dibromo-1-methoxy-                                                                     0    9   9   9  0    0                                           2-(alpha,alpha,alpha-                                                         trifluoro-p-tolyl)-                                                           pyrrole-3-carbonitrile                                                        __________________________________________________________________________     .sup.1 SCRW = Southern Corn Rootworm                                     

The above test results show the efficacy of the compounds asinsecticides and acaricides.

EXAMPLE 19

The following tests show the efficacy of the compounds as insecticides.All tests are performed using technical materials and kept at 27° C. Thetest concentrations are in terms of active ingredient.

Heliothis virescens, 3rd instar tobacco budworm

Cotton cotyledons are dipped in the test formulation and allowed to dryin a hood. When dry, each is cut into quarters and ten sections placedindividually in 30 mL plastic medicine cups containing a 5 to 7 mm longpiece of damp dental wick. One 3rd instar caterpillar is added to eachcup and a cardboard lid placed on the cup. Treatments are maintained for3 days before mortality counts and estimates of reduction in feedingdamage are made.

Empoasca abrupta, adults, western potato leafhopper

A Sieva lima bean leaf about 5 cm long is dipped in the test formulationfor 3 seconds with agitation and placed in a hood to dry. The leaf isplaced in a 100×10 mm petri dish containing a moist filter paper on thebottom. About 10 adult leafhoppers are added to each dish and thetreatments are kept for 3 days before mortality counts are made.

Blattella germanica, bait test, adult male German cockroach

A 0.1% bait is prepared by pipetting 1 mL of a 1000 ppm solution of thetest compound in acetone onto 1 gram of cornmeal in a 30 mL wide-mouthbottle. The bait is dried by passing a gentle stream of air into thebottle. The bait is placed in a 1 pint widemouth Mason jar and 10 adultmale cockroaches are added. A screen lid is placed on the jar and asmall piece of cotton soaked in 10% honey is put on the top of thescreen lid. Mortality counts are made after 3 days.

Blattella germanica, residue test, adult male German cockroach

One mL of a 1000 ppm acetone solution of the test material is pipettedslowly over the bottom of a 150×15 mm petri dish so as to give asuniform coverage as possible. After the deposit has dried, 10 adult malecockroaches are placed in each dish and the lid is added. Mortalitycounts are made after 3 days.

Spodoptera eridania, systemic uptake, 3rd instar larvae, southernarmyworm

The compound is formulated as an emulsion containing 0.1 gm of the testmaterial, 0.2 gm of Emulphor EL-620, emulsifier, 10 mL of acetone and 90mL of water. This is diluted 10-fold with water to give a 100 ppmemulsion for test. Subsequent 10-fold dilutions are made with water asneeded. Sieva lima bean plants, with the primary leaves expanded to alength of 7 to 8 cm, are cut off at least 3 cm above the soil level toavoid contamination with soil bacteria that will cause decay of the stemduring the test. The cut stems are placed in the test emulsions and eachstem is wrapped with a bit of cotton to hold the stem off the bottom ofthe bottle and to limit evaporation and volatilization of the compound.The test is maintained for 3 days at 27° C. to allow the compounds to betaken up into the plant. Following this, one leaf is removed from theplant and placed in a 100×10 mm petri dish with 10 southern armyworms.Mortality counts and observations of feeding damage are made 3 and 5days later.

Empoasca abrupta, adults, western potato leafhoppers, systemic uptake

The compound is formulated as an emulsion containing 0.1 gm of the testmaterial, 0.2 gm of Emulphor EL-620, emulsifier, 10 mL of acetone and 90mL of water. This is diluted 10 fold with water to give a 100 ppmemulsion for the test. Subsequent 10-fold dilutions are made with wateras needed. Sieva lima bean plants, with the primary leaves expanded to alength of 7 to 8 cm, are cut off at least 3 cm above the soil level toavoid contamination with soil bacteria that will cause decay of the stemduring the test. The cut stems are placed in the test emulsion and eachstem is wrapped with a bit of cotton to hold the stem off the bottom ofthe bottle and to limit evaporation and volatilization of the compound.The test is maintained for 3 days at 27° C. to allow the compounds to betaken up into the plant. Following this, one leaf is removed from theplant and placed in a 100× 10 mm petri dish with 10 adult western potatoleafhoppers. After 3 days, mortality counts are made.

The rating scale for the above evaluations is the same as described inExample 18.

The data obtained are reported in Table II.

                                      TABLE II                                    __________________________________________________________________________    Insecticide Evaluations                                                                     LEAF            G. COCKROACH                                                  HOPPER                                                                              Tobacco Budworm                                                                         Bait Res                                                      (ppm) (ppm)                                                                              (ppm)                                                                              (ppm)                                                                              (ppm)                                      Compound      100   1000 100  1000 1000                                       __________________________________________________________________________    4,5-Dibromo-2-( -p-chloro-                                                                  9     9    0    0    8                                          phenyl)-1-hydroxypyrrole-                                                     3-carbonitrile                                                                4,5-Dichloro-2-( -p-chloro-                                                                 9     9    0    0    0                                          phenyl)-1-hydroxypyrrole-                                                     3-carbonitrile                                                                4,5-Dibromo-2-( -p-chloro-                                                                  0     9    0    0    0                                          phenyl)-1-methoxypyrrole-                                                     3-carbonitrile                                                                4,5-Dibromo-2-( -p-chloro-                                                                  0     9    0    0    0                                          phenyl)-1-(ethoxymethoxy)-                                                    pyrrole-3-carbonitrile                                                        4,5-Dibromo-2-( -p-chloro-                                                                  --    0    0    0    0                                          phenyl)-1-hydroxypyrrole-                                                     3-carbonitrile, dimethyl                                                      carbamate (ester)                                                             4,5-Dibromo-2-( -p-chloro-                                                                  --    9    0    0    0                                          phenyl)-1-hydroxypyrrole-                                                     3-carbonitrile, acetate                                                       (ester)                                                                       2-( -p-Chlorophenyl)-1-                                                                     0     8    0    0    0                                          methoxy-5-nitropyrrole-                                                       3-carbonitrile                                                                2-( -p-Chlorophenyl)-1-                                                                     0     0    0    0    0                                          methoxy-4-nitropyrrole-                                                       3-carbonitrile                                                                2-( -p-Chlorophenyl)-1-                                                                     --    0    --   0    0                                          methoxypyrrole-3,4-                                                           dicarbonitrile                                                                2-Bromo-5-( -p-Chloro-                                                                      0     3    3    0    0                                          phenyl)-1-methoxy-  R3   R3                                                   pyrrole-3,4-dicarbo-                                                          nitrile                                                                       4,5-Dichloro-2-( -p-chloro-                                                                 --    9    9    0    0                                          phenyl)-1-methoxypyrrole-                                                     3-carbonitrile                                                                4-Bromo-5-( - p-chloro-                                                                     0     --   9    0    --                                         phenyl)-1-methoxy-2-                                                          (trifluoromethyl)-                                                            pyrrole-3-carbonitrile                                                        5-( -p-Chlorophenyl)-1-                                                                     7     9    9    7    4                                          methoxypyrrole-2,3-                                                           dicarbonitrile                                                                4-Bromo-5-( -p-chloro-                                                                      0     9    9    0    4                                          phenyl)-1-methoxy-                                                            pyrrole-2,3-dicarbo-                                                          nitrile                                                                       3,3-Dimethylbutyric acid,                                                                   0     0    0    0    0                                          2,3-dibromo-5-( -p-chloro-                                                    phenyl)-4-cyanopyrrol-1-                                                      yl ester                                                                      Pivalic acid, 2,3-di-                                                                       0     9    4    0    0                                          bromo-5-( -p-chlorophenyl)-                                                   4-cyanopyrrol-1-yl ester                                                      4,5-Dibromo-2-( -p-chloro-                                                                  0     9    9    0    0                                          phenyl)-1-(cyanomethoxy)-                                                     pyrrole-3-carbonitrile                                                        4,5-Dibromo-2-( -p-chloro-                                                                  0     9    0    0    0                                          phenyl)-1-(2-propynyloxy)-                                                    pyrrole-3-carbonitrile                                                        4,5-Dibromo-2-( -p-chloro-                                                                  0     8    0    0    0                                          phenyl)-1-(1-methoxy                                                          ethoxy)pyrrole-3-carbo-                                                       nitrile                                                                       4,5-Dibromo-2-(3,4-                                                                         0     9    4    0    7                                          dichlorophenyl)-1-                                                            hydroxypyrrole-3-                                                             carbonitrile                                                                  4,5-Dibromo-2-(3,4-                                                                         0     9    0    0    2                                          dichlorophenyl)-1-                                                            methoxypyrrole-3-                                                             carbonitrile                                                                  4,5-Dibromo-2-(3,4-                                                                         0     9    0    0    0                                          dichlorophenyl)-1-                                                            (ethoxymethoxy)-                                                              pyrrole-3-carbonitrile                                                        4,5-Dichloro-2-                                                                             0     9    0    0    8                                          ( -p-chlorophenyl)-1-                                                         (ethoxymethoxy)-                                                              pyrrole-3-carbonitrile                                                        4,5-Dichloro-2-( -p-chloro-                                                                 0     9    7    0    0                                          phenyl)-1-(2-propynyloxy)-                                                    pyrrole-3-carbonitrile                                                        4,5-Dichloro-2-( -p-chloro-                                                                 0     9    9    0    5                                          phenyl)-1-(cyanomethoxy)-                                                     pyrrole-3-carbonitrile                                                        4,5-Dichloro-2-(3,4-                                                                        5     9    9    0    9                                          dichlorophenyl)-1-                                                            methoxypyrrole-3-                                                             carbonitrile                                                                  4,5-Dichloro-2-(3,4-                                                                        0     9    9    0    9                                          dichlorophenyl)-1-                                                            hydroxypyrrole-3-                                                             carbonitrile                                                                  4,5-Dichloro-1-                                                                             3     9    9    0    0                                          (cyanomethoxy)-2-                                                             (3,4-dichlorophenyl)-                                                         pyrrole-3-carbonitrile                                                        2,4-Dibromo-5-( -p-chloro-                                                                  0     --   0    --   --                                         phenyl)-1-methoxy-                                                            pyrrole-3-carbonitrile                                                        1-(Benzyloxy)-4,5-                                                                          0     --   0    --   --                                         dichloro-2-( -p-chloro-                                                       phenyl)-pyrrole-3-                                                            carbonitrile                                                                  3,4-Dibromo-5-(3,4-                                                                         4     9    8    0    0                                          dichlorophenyl)-1-                                                            methoxypyrrole-2-                                                             carbonitrile                                                                  4,5-Dibromo-1-hydroxy-                                                                      0     9    4    0    7                                          2-(alpha,alpha,alpha-                                                         trifluoro-p-tolyl)-                                                           pyrrole-3-carbonitrile                                                        4,5-Dibromo-1-methoxy-                                                                      2     8    6    0    0                                          2-(alpha,alpha,alpha-                                                         trifluoro-p-tolyl)-                                                           pyrrole-3-carbonitrile                                                        __________________________________________________________________________

EXAMPLE 20 Evaluation of test compounds as nematicidal agents

Cultural Maintenance: Cultures of C. Elegans are maintained on E. colilawns on NG Agar Plates at 20° C. New cultures are established weekly.

Nematodes for testing are washed from 4-5 day old cultures using FreshAscaris Ringers Solution (FARS). The worms are further washed with FARS,containing gentamycin, to reduce bacterial contamination and centrifugedto separate worms from wash solution. This procedure is repeated 3times. The washed worms are then added to C. briggsae Maintenance Medium(CbMM), from GIBCOa to which is added gentamycin (600 units/mL) andmycostatin (0.5 mg/mL).

The tests are then made with mixtures of three compounds, piggy-backedfrom another high capacity screening program to reduce additional laborand compound expenditures.

Compounds are dissolved in acetone and made up to volume with water. Thefinal test concentration of each compound in the mixture is 150 ppm. Thetest material is micropipetted (25 ul) into a single well of a 96-wellsterile tissue culture plate (COSTAR)^(b) and the solvent allowed toevaporate. These "treated" plates are used immediately or stored in afreezer without apparent adverse effects on the compounds.

A freshly prepared volume (50 ug) of C. elegans in CbMM is micropipettedinto each treated well and several control wells per plate. Cultureplates are incubated at 20° C.

Observations for efficacy are made under a dissecting microscope at 4,24 and 48 hours post-immersion. Immediately prior to reading the plate,it is gently tapped to stimulate the movement of the worms. Activity isjudged subjectively, but semi-quantitatively, based on the drug effectson motility of the adults and larvae. The criteria are as follows: 9=nomotality, 8=no motality, 7=markedly reduced motility in approximately95% of worms, 6=reduced motility, 5=slightly reduced motility, 0=normalmotility, same as controls. Other factors indicating activity are easilynoted such as death, rigor mortis, contraction, coiling, paralysis,abnormal twitching, reduced worm population in 48 hours and otherdeviation from normal behavior.

    ______________________________________                                        PROCEDURE FOR CAENORHABDITIS ELEGANS ASSAY                                    ______________________________________                                        Day 0    Inoculate E. Coli-NG Agar Dish With 30-50                                     C. Elegans                                                                    Incubate At 20° C.                                            Day 4    Harvest New C. Elegans Population                                             Wash With Antibiotics                                                         Transfer to CbMM                                                              Add C. Elegans (25-100 UL) to "Medicated"                                     Wells.sup.a                                                                   Observe For Activity At 4 Hours Post-Immer-                                   sion                                                                 Day 5    Observe For Activity                                                 Day 6    Observe For Activity                                                 ______________________________________                                         .sup.a Medicated Wells May Be Prepared Fresh Or Earlier And Stored In         Freezer                                                                  

Data obtained in these tests are reported in Table III below.

                  TABLE III                                                       ______________________________________                                        Nematicidal Evaluation                                                                           C. Elegans                                                                    (150 ppm)                                                                     LARVA  ADULT                                               ______________________________________                                        4,5-Dichloro-2-( -p-chlorophenyl)-                                                                 7        7                                               1-hydroxypyrrole-3-carbonitrile                                               4,5-Dichloro-2-( -p-chlorophenyl)-                                                                 8        8                                               1-(cyanomethoxy)pyrrole-3-                                                    carbonitrile                                                                  4,5-Dichloro-1-(cyanomethoxy)-                                                                     9        9                                               2-(3,4-dichlorophenyl)pyrrole-                                                3-carbonitrile                                                                2,4-Dibromo-5-( -p-chlorophenyl)-                                                                  0        0                                               1-methoxypyrrole-3-carbonitrile                                               2-( -p-Chlorophenyl)-1-methoxy-                                                                    0        0                                               4-nitropyrrole-3-carbonitrile                                                 ______________________________________                                    

What is claimed is:
 1. A compound useful in the preparation ofN-oxygenated arylpyrroles having the structural formula: ##STR51##wherein X is H or CF₃ ;L is H, F, Cl or Br; M and R are eachindependently H, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₃ alkylthio, C₁ -C₃alkylsulfinyl, C₁ -C₃ alkylsulfonyl, cyano, F, Cl, Br, I, nitro, CF₃, R₁CF₂ Z, R₂ CO or NR₃ R₄ ; and when M and R are on adjacent positions andtaken with the carbon atoms to which they are attached they may form aring in which MR represents the structure: ##STR52## Z is S(O)_(n) or O;R₁ is H, F, CHF₂, CHFCl or CF₃ ;R₂ is C₁ -C₃ alkyl, C₁ -C₃ alkoxy or NR₃R₄ ; R₃ is H or C₁ -C₃ alkyl; R₄ is H, C₁ -C₃ alkyl or R₅ CO; R₅ is H orC₁ -C₃ alkyl; and n is an integer of 0, 1 or 2; and R₆ is hydrogen, C₁-C₆ alkyl or C₃ -C₆ cycloalkyl.